Europaisches Patentamt European Patent Office © Publication number: 0 059 457 Office europeen des brevets A1
© EUROPEAN PATENT APPLICATION
© Application number: 82101503.9 ©mtci.3: C 07 C 47/347 C 07 C 47/45, C 07 C 31/137 @ Date of filing: 26.02.82 C 07 C 33/16, A 61 K 7/46 C 07 C 29/38, C 07 C 45/41 C 07 C 45/50, C 07 C 45/58 C 07 C 45/62
© Priority: 28.02.81 JP 29188/81 © Applicant: Nippon Petrochemicals Co., Ltd. 28.02.81 JP 29189/81 Saiwai Building, 1-3-1 Uchisaiwai-cho Chiyoda-ku 22.08.81 JP 131743/81 Tokyo(JP) 22.08.81 JP 131744/81 © Inventor: Inoue, Yoshiharu 16-24, Imaichi 2-chome Asahi-ku © Date of publication of application: Osaka-shi Osaka-fu(JP) 08.09.82 Bulletin 82736 © Inventor: Tanimoto, Fumio 471, Muromachi Nishiiru © Designated Contracting States: Santeicho CH DE FR GB LI NL Nakadachiuri-dori Kamigyo-ku Kyoto-shi Kyoto-fu(JP) © Inventor: Kitano, Hisao 1-6-205, Harimacho 3-chome Abeno-ku Osaka-shi Osaka-f u(JP)
© Representative: Schubel-Hopf, Ursula, Dr. et al, K.L. Schiff Dr. A. v. Funer Dipl.-lng. P. Strehl Dr. U. Schubel-Hopf Dipl.-lng. D. Ebbinghaus Dr.lng. D .Finck Patentanwalte Mariahilf platz 2 & 3 D-8000 Munchen 90(DE)
© Derivatives of norbornanes having hydrocarbon side chains, processes for preparing the same and perfume compositions containing the same. Norbornane© Norbornane derivatives having hydrocarbon side chains, the processes for preparing the same and perfume compositions containing the same. The norbomanenorbornane deriva-(I)� tives are represented by the following general formula (I) (11) 3 wherein R4 is a methyl group, an ethyl group,group,gn a n-propyl a ,(1) 1 » group or an isopropyl group, and X is a carboncarl atom of the norbomanenorbornane ring. The above norbornane derivativesde give a wide variety of woody fragrances and are usefului as compo- nents for various perfume products. in 1 wherein C2 is an ethyl group, an ethylidene group or a vinyl group each connected to 5 or 6 position of the norbornane 0) ring, each of R, and R2 is a hydrogen atom or a methyl group, and R3 is a formyl group or a group represented by the o following general formula (II)
Q. LU Croydon Printing Company Ltd. BACKGROUND OF THE INVENTION
1. Field of the Invention
. This invention relates to derivatives of norbornanes, processes for preparing the same and perfume compositions containing the.same. More particularly, the invention relates to novel derivatives of norbornanes having hydrocarbon side chains, especially, saturated or unsaturated hydrocarbons containing two carbon atoms, processes for preparing the same and perfume compositions containing the same.
2. Description of the Prior Art
A variety of synthetic perfume components have been prepared in order to make up for or to use in place of
expensive natural perfume components. For example,
compounds having norbornane bicyclo-(2,2,1)-heptane ring
are proposed in several references.
U.S. Patent No. 3,673,261 and No. 3,673,263
disclose 2-methyl-3-(5'-hydroxyalkenyl)-norbornanes.
U.S. Patent No. 3,748,344 discloses a process for preparing
cyclic acetals of norbornane carboxyaldehydes. U.S. Patent
No. 3,860,635 discloses a process for preparing.vinyl
norbornanone. Further, disclosed in U.S. Patent No. 4,076,853
are various kinds of alpha-allyl or methallyl-3,3-dimethyl-
2-norbornyl methanols. However, in connection with the specific
norbornane derivatives having hydrocarbon side chains containing two carbon atoms of the present invention, no disclosure is found.
BRIEF SUMMARY OF THE INVENTION
The present invention is based upon the fact
that the inventors found novel norbornane derivatives, processes for preparing the same and perfume compositions
containing the same, as described below.
The object of the present invention is, therefore,
to provide such a new finding.
The present invention relates to derivatives
of norbornanes having hydrocarbon side chains, processes
for preparing the same and perfume compositions containing
the same. The norbornane derivatives of the invention are
represented by the following general formula (I)
wherein C2 is an ethyl group, an ethylidene group or a vinyl
group each connected to 5 or 6 position of the norbornane
ring, the dashed line connected to C2 is a single bond when
C2 is an ethyl group or a vinyl group and a double bond when
C2 is an ethylidene group, each of R1 and R2 is a hydrogen
atom or a methyl group, and R3 is a formyl group or a group
represented by the following general formula (II) wherein R4 is a methyl group, an ethyl group, a n-propyl group or an isopropyl group, the combination of a solid line with a dotted line indicates a single bond or a double bond, and
X is a carbon atom of the norbornane ring.
According to the present invention, the norbornane derivatives represented by the foregoing general formula (I) can be prepared by hydrolyzing and decarboxylating glycidic esters represented by the following general formula (III) at temperatures in the range of 0 to 250°C
wherein C2, dashed line, R1and R2 are respectively the same as those in the foregoing general formula (I) and R5 is a hydrocarbon group having 1 to 6 carbon atoms. Through this process, a norbornane derivative of formula (I) having a formyl group as R3 can be prepared.
The inventors have found another method to prepare the norbornane derivative of formula (I) having a formyl group as R3 by reacting 2-norbornene represented by the following general formula (IV) with carbon monoxide and hydrogen gas in the presence of a catalyst at temperatures in the range of 30 to 300°C
wherein C2, dashed line and R1 are respectively the same as those in the formula (I). The reaction product.in this process has a hydrogen atom as R2 and'a formyl group as R3 in the foregoing general formula (I).
Further, when R3 is not a formyl group but a group represented by the foregoing general formula (II), the product obtained from any one of the above processes, that is, a norbornyl aldehyde, is reacted with ethyl alkyl ketone in the presence of an aldol condensation catalyst at temperatures in the range of 0 to 200oC and thereafter the reaction product is subjected to dehydration and reduction, thereby obtaining the norbornane derivative of formula (I) having a group of formula (II) as R3.
Also included in the present invention is perfume compositions containing the norbornane derivatives representec by the above-defined formula (I).
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described in more detail.
As described above, the norbornane derivatives of the present invention are represented by the following general formula (I) wherein C2 is an ethyl group, an ethylidene group or a vinyl group each connected to 5 or 6 position of the norbornane ring, the dashed line connected to C2 is a single bond when
C2 is an ethyl group or a vinyl group and a double bond when
C2 is an ethylidene group, each of R1 and R2 is a hydrogen atom or a methyl group, and R3 is a formyl group or a group represented by the following general formula (II)
wherein R4 is a methyl group, an ethyl group, a n-propyl group
or an isopropyl group, the combination of a solid line with
a dotted line indicates a single bond or a double bond, and
X is a carbon atom of the norbornane ring.
The compounds included in the above norbornane
derivatives represented by the general formula (I) are:
5- or 6-ethylnorbornyl-2-aldehyde,
5- or 6-ethylidenenorbornyl-2-aldehyde,
5- or 6-vinylnorbornyl-2-aldehyde,
their 3-methyl derivatives and 3,3-dimethyl derivatives, and
4-(5'- or 6'-ethylnorbornan-2'-yl)-3-methylbutan-2-ol,
4-(5'- or 6'-ethylidenenorbornan-2'-yl)-3-methylbutan-2-ol, 4-(5'- or 6'-vinylnorbornan-2'-yl)-3-methylbutan-2-ol,
4-(5'- or 6'-ethylnorbornan-2'-yl)-3-methyl-3-buten-2-ol,
4-(5'- or 6'-ethylidenenorbornan-2'-yl)-3-methyl-3-buten-2-ol,
4-(5'- or 6'-vinylnorbornan-2'-yl)-3-methyl-3-buten-2-ol,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2-methylpentan-3-ol,
1-(5'- or 6'-ethylidenenorbornan-2'-yl)-2-methylpentan-3-ol,
1-(5'- or 6'-vinylnorbornan-2'-yl)-2-methylpentan-3-ol,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2-methyl-1-penten-3-ol,
1-(5'- or 6'-ethylidenenorbornan-2'-yl)-2-methyl-1-penten-3-ol,
1-(5'- or 6'-vinylnorbornan-2'-yl)-2-methyl-l-penten-3-ol,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2,4-dimethylpentan-3-ol,
1-(5'- or 6'-ethylidenenorbornan-2'-yl)-2,4-dimethyl- pentan-3-ol,
1-(5'- or 6'-vinyInorbornan-2'-yl)-2,4-dimethylpentan-3-ol,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2,4-dimethyl-1-penten-3-ol,
1-(5'- or 6'-ethylidenenorbornan-2'-yl)-2,4-dimethyl-1- penten-3-ol,
1-(5'- or 6'-vinylnorbornan-2'-yl)-2,4-dimethyl-1-penten-3-ol,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2-methylhexan-3-ol,
1-(5'- or 6'-ethylidenenorbornan-2'-yl)-2-methylhexan-3-ol,
1-(5'- or 6'-vinylnorbornan-2'-yl)-2-methylhexan-3-ol,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2-methyl-l-hexen-3-ol,
1-(5'- or 6'-ethylidenenorbornan-2'-yl)-2-methyl-l-hexen-3-ol,
1-(5'- or 6'-vinylnorbornan-2'-yl)-2-methyl-1-hexen-3-ol, their 3'-methyl derivatives and 3',3'-dimethyl derivatives. The above norbornane derivatives according to the present invention have woody odors as their fundamental note, and vary from fragrant tone to deep tone with their structures. They may be favorably formulated with not only woody notes but also floral, fougere, mossy, spicy, chypre, leather, tobacco, animal, citrus, resinous, green, aldehydic or the like to give various fragrant, perfumes and flavors.
Accordingly, the norbornane'derivatives of the present invention are of great importance as bases for various perfume compositions, which may be employed to provide fragrance in perfumes, cosmetics, detergents, house- hold products, toiletries, bleaches, antiperspirants, deodorants, aerosol products, bath preparation and the aromatic goods.
They may also be applied widely to flavor components, artifi- cial essential oil components, perfume extenders and the like.
One of the typical methods for preparing the norbornane derivatives according to the present invention is as follows: a glycidic ester represented by the following general formula (III) is hydrolyzed and decarboxylated at temperatures in the range of 0 to 250°C
wherein the definitions for C2, dashed line-, R1, R2 and R5
are the same as those previously defined.
Hydrolysis of the above glycidic ester may be carried out in an acidic agueous solution or a basic aqueous solution. It is, however, generally carried out in a basic condition because the hydrolysis proceeds more easily.
As the reaction medium; water and an alcohol, for example, a mixture of water and ethyl alcohol is employed. Used as basic materials are alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alcoholates such as sodium methylate, alkaline carbonates and anion exchange resins. The temperatures for hydrolysis should be in the range of 0 to 100°C.
The glycidic ester is hydrolyzed under a basic condition to afford, in general., the glycidic acid salt, which is converted into glycidic acid by adding a mineral acid such as hydrochloric acid and it is then subjected to decarboxylation at temperatures in the range of 0 to 250°C.
When the decarboxylation is carried out at temperatures lower than 0°C, the reaction is difficult to proceed. On the other hand, when the reaction temperature is higher than 250°C, the decarboxylation is accompanied by side reactions such as decomposition and polymerization to a considerable extent.
A preferable range of the decarboxylation temperature is 10 to 150°C. Heating during the decarboxylation may be continued until the evolution of carbon dioxide ceases. This heating time is generally 0.5 to 5 hours. Incidentally, the hydro- carbon group R5 having more than 6 carbon atoms of the foregoing general formula (III) is not desirable because the decarboxylation becomes difficult. After the above-described reaction, the reaction product is separated from the reaction mixture by means of suitable operations such as extraction or distillation and the reaction product is further purified to obtain the norbornane derivative of general formula (I) having a formyl group as the group R3.
.The glycidic esters represented by the foregoing general formula (III) can be prepared by reacting the norbornanone represented by the following general formula (V) with alkyl monohalogenoacetates such as alkyl chloroacetate and alkyl bromoacetate in the presence of a basic catalyst, permitting dehydrohalogenation
wherein C2, dashed line, R1 and R2 are the same as those in
formula (I). The alkyl groups of the alkyl monohalogenoacetates
are exemplified by methyl, ethyl, propyl, isopropyl, butyl,
sec-butyl, amyl, isoamyl, hexyl, 2-ethylhexyl and cyclohexyl
groups.
In the above dehydrohalogenation, when the carbon
atom number of the alkyl group of the alkyl monohalogenoacetate
lies from 1 to 6, considerably smooth reaction can be
accomplished, because the hydrolysis of the glycidic ester
and subsequent decarboxylation can be easily performed.
When the carbon atom number of the alkyl group of the alkyl monohalogenoacetate is 7 or more, the dehydrohalogenation, hydrolysis and decarboxylation require much time, which is economically disadvantageous from the industrial point of view. It is, therefore, preferable to use the alkyl monohal- ogenoacetate in which the alkyl group has 1 to 6 carbon atoms.
Commercially available alkyl monohalogenoacetates are exemplified by methyl chloroacetate, ethyl chloroacetate,
isopropyl chloroacetate and ethylene bis(chloroacetate).
The norbornane derivatives of formula (I) having a formyl group as R3 of the same formula may be prepared by an alternative method. That is, the norbornene represented by the following general formula (IV) is reacted with carbon monoxide and hydrogen gas in the presence of a catalyst at temperatures in the range of 30 to 300°C.
Exemplified as compounds of the above formula (IV) are 5-ethyl-2-norbornene, 5- or 6-ethyl-3-methyl-2-norbornene,
5-vinyl-2-norbornene, 5- or 6-vinyl-3-methyl-2-norbornene,
5-ethylidene-2-norbornene and 5- or 6-ethylidene-3-methyl-
2-norbornene.
The above reaction is represented by the following reaction formula: As the products in the above reaction, a norbornane
derivative having a formyl group at the neighboring
position of R1 in the norbornane ring and other by-product
are also produced in addition to the norbornane derivative
represented by the foregoing formula (I') having a formyl group as R3. Accordingly, it is of great importance to
select the catalyst in order to obtain the maximum yield of
the norbornyl-2-aldehyde of formula (I'), the aimed product of
the invention.
In accordance with the results of many experiments,
it has been found that transition metal compounds can be used
in order to complete the above reaction and, especially, the
compounds of group VIII elements of the periodic table are
advantageously employed.
Among the group VIII metal compounds, those of
cobalt, rhodium, iridium, ruthenium and platinum are
preferable. When the complexes of carbonyl compounds of
these metals are used, it is, of course, important to give
consideration to the kind of ligands to be coordinated in
order to improve the selectivity in the reaction, in which
electron donating properties and steric factors should also be taken into account.
Some of metal carbonyl compounds are commercially available, however, they can be prepared before use by react- ing activated metal powder or other metal compounds with carbon monoxide. In order to improve catalytic activity, the following compounds may be coordinated with these carbonyl complexes or added to the reaction system. There are tertiary amines, phosphines and phosphites as such ligands. Especially, in the hydroformylation of the present invention, adduct complexes of tertiary phosphines such as tributyl phosphine and triphenyl phosphine are quite useful for improving the selectivity of the aimed products. Among the above-mentioned metal compounds, cobalt compounds and rhodium compounds are preferable. They can be used singly or in combination with other metal compounds as a promoter.
When the above metal compounds are used, reaction temperatures may be in the range of 30 to 300 C, more pre- ferably 50 to 250°C. Reaction pressures are generally in the range of 1 to 450 kg/cm .
The molar ratio of carbon monoxide to hydrogen that are introduced into the reaction system can be varied within the range of 1:1 to 1:4, however, the ratio of 1:1 is commonly used.
The hydroformylation is usually carried out in a liquid phase using a reaction medium. Exemplified as such reaction media are one or a mixture of saturated hydrocarbons, aromatic hydrocarbons such as benzene, ethers, alcohols, esters, sulfolanes, water and reaction materials themselves.
In the hydroformylation procedure, the above
2-norbornene is charged together with carbon monoxide, hydrogen gas and the reaction medium into an autoclave and the reaction is carried out in the presence of a catalyst by heating at a predetermined temperature. After the reaction is completed, an excess of carbon monoxide and hydrogen gas are purged from the vessel and the catalyst is removed or decomposed through an appropriate method. After that, .the reaction product is further treated by, for example, fractional distillation to obtain the aimed norbornane derivative.
When the group C2 is an ethylidene group or a vinyl group in the foregoing glycidic ester of general formula (III) or the norbornane of general formula (IV), the corresponding norbornane derivative of general formula (I) having an ethylidene group or a vinyl group as C2 will be obtained. In the case where a norbornane derivative of general formula (I) having an ethyl group as C2 is desired as the final product, the group C2 of the above reaction product is further subjected to partial hydrogenation.
In this partial hydrogenation, the formyl group
is not reduced but the ethylidene group or vinyl group is
selectively hydrogenated into an ethyl group. This reaction
may be carried out by catalytic hydrogenation or by using a
reducing agent. As catalysts for the catalytic hydrogenation,
the group VIII metals of the periodic table such as palladium, platinum, rhodium, and their compounds are preferably used. These catalysts may be deposited on a carrier such as a charcoal. The reaction pressure is in the range of ordinary pressure to 50 kg/cm2 of hydrogen and the reaction temperature is in the range of -10 to 200°C. As reaction media, alcohols such as ethyl alcohol, saturated hydro- carbons such as hexane, aromatic hydrocarbons such as benzene, and esters such as ethyl acetate may be used.
When the partial hydrogenation is carried out by using a nickel catalyst or a reducing agent such as diimide, the formyl group of ethylidene- or vinylnorbornyl-
2-aldehyde is protected by converting it into acetal. After the hydrogenation, the reaction product is subjected to acidic hydrolysis to regenerate the aldehyde.
It-is known that ethylnorbornyl-2-aldehyde is obtained through the Diels-Alder reaction between an alkylcyclopentadiene and acrolein. However, in this case, many kinds of the Diels-Alder reaction by-products are formed and the yield of the aimed product is not good.
Therefore, this method may be disadvantageous in a commercial production.
When the final product of the foregoing general formula (I) has a group of R3 other than a formyl group and the group R3 is represented by the foregoing general formula (II), the final product is prepared by reacting the above-described norbornyl-2-aldehydes with ethyl alkyl keton in the presence of an aldol condensation catalyst at temperatures in the range of 0 to 200°C, which is followed by dehydration and reduction.
The above-mentioned ethyl alkyl ketones used in the aldol condensation with the above norbornyl-2-aldehyde are exemplified by ethyl lower-alkyl ketones such as methyl ethyl ketone, diethyl ketone, ethyl propyl ketone and ethyl isopropyl. ketone.
In the aldol condensation, acidic and basic
substances are used as catalysts. The acidic catalysts may
include inorganic acids such as sulfuric acid, hydrochloric
acid, phosphoric acid and hydrobromic acid, Lewis acids such
as boron trifluoride, and organic acids such as benzene sulfonic
acid, trifluoromethane sulfonic acid, toluene sulfonic acid,
naphthalene sulfonic acid, trifluoroacetic acid, trichloro-
acetic acid and sulfamic acid. The basic catalysts
may include metal hydroxides such as lithium hydroxide,
sodium hydroxide, potassium hydroxide, barium hydroxide
and calcium hydroxide, metal alkoxides such as lithium
methylate, sodium methylate, sodium ethylate, potassium
methylate, aluminum isopropoxide and potassium tert-butoxide,
and weak basic compounds such as sodium carbonate, potassium
carbonate, potassium acetate and potassium fluoride. Further
exemplified as the basic catalysts are sodium hydride,
lithium hydride, potassium hydride, lithium amide, sodium
amide, potassium amide, tertiary amines, quaternary ammonium
salts, active methylene alkali compounds, alkali fluorides,
alkali metal oxides, alkaline earth metal oxides and cyclic amines. Among them, alkali hydroxides, alkali carbonates, alkali alkoxides, alkali amides, tertiary amines, cyclic amines and alkali salts of weak organic acids are important for industrial production.
The temperature of the aldol condensation is in the range of 0 to 200°C, preferably 50 to 150°C and the pressure may be any of the atmospheric pressure, elevated pressures or reduced pressures as far as the reaction temper- ature is maintained within a predetermined range.
The reaction may be carried out without any reaction medium, but reaction media can, of course, be used so as to bring reaction materials into sufficient contact with catalyst and to make reaction temperature uniform.
Used as such reaction media are an excess amount of ketones themselves, alcohols, water, saturated hydrocarbons, ethers,. and halogenated hydrocarbons. They can be employed singly or in combination of two kinds or more.
In this process, the hydrogenation is performed after the aldol condensation of norbornyl-2-aldehyde and ethyl alkyl ketone, however, when reaction conditions are properly selected,, the aldol condensation is generally followed by spontaneous dehydration. In this case, there is no need for the dehydration process. However, according to selected reaction conditions, for example,-when the temperature of condensation is relatively low, the dehydra- tion may be readily carried out by heating with or without adding a dehydrating agent. Through the above-described processes, the ketones represented by the general formulae (VI) and (VII) in the following reaction scheme are obtained. Shown in this reaction scheme are the cases where norbornyl-2-aldehydes of general formula (I"), that is, the norbornane derivatives of general formula (I) having hydrogen atoms as R1 and R2, are reacted with diethyl ketone to produce reaction products of general formulae (VI) and (VII), which are then reduced.
In the reaction scheme, the symbol C2 indicates an ethylidene group or a vinyl group. As shown in the reaction scheme, the norbornane derivatives of the present invention as represented by the general formulae (IX), (X),
(XI) and (XII) can be prepared by reducing the ketones of general formulae (VI) and (VII).
In this reaction scheme, it should be noted that only the carbonyl groups are selectively reduced into the hydoxy groups in steps (B), (C), (G) and (H).
In these steps, metal hydrides, aluminum alkoxides and alcohols, or alkoxides of alkali metals or alkaline earth metals and alcohols are advantageously used as reducing agents. Further, the reduction may be carried out by catalytic hydrogenation in the presence of a suitable catalyst under mild conditions, or it may also be carried out by an electrolytic reduction.
Exemplified as the above-mentioned metal hydrides are sodium borohydride, lithium borohydride, lithium aluminum hydride, sodium aluminum hydride, aluminum hydride complex, lithium hydride, sodium hydride, calcium hydride and bis(methoxyethyl)aluminum sodium hydride. An example of the combination of alcohol and aluminum alkoxide is a combination of isopropyl alcohol and aluminum isopropoxide.
As the media for reduction using these reducing
agents, one or a mixture of two or more of alcohols such as
methyl alcohol, ethyl alcohol and isopropyl alcohol,, ethers
such as dioxane, diethyl ether, ethylene glycol dimethyl
ether and tetrahydrofuran, saturated aliphatic hydrocarbons,
aromatic solvents such as toluene, and aliphatic alkyl esters
may be used.
The temperature of reduction is generally in the
range of 0 to 150°C. After the reduction, unreacted materials
and reaction medium are separated to collect the organic layer containing the aimed product, which is further subjected to purification such as fractional distillation to obtain the final product.
In the steps of (A), (D), (H) and (J) in the fore- going reaction scheme, the carbon-carbon double bonds are reduced while carbonyl groups and hydroxy groups remain uneffected. Therefore, this reduction is carried out by catalytic hydrogenation under mild conditions. Exemplified as preferable catlysts for this catalytic hydrogenation are group VIII metals of the periodic table such as nickel, cobal ruthenium, rhodium or platinum. They may be conveniently use on carriers such as barium sulfate, alumina or calcium carbonate. The pressure of this catalytic hydrogenation may be in the range of ordinary pressure to 10 kg/cm2 and the reaction temperatures may be in the range of 0 to 150°C.
In the reducing steps (E) and (F) of the foregoinc reaction scheme, the reduction of carbon-carbon double bonds into single bonds and the reduction of carbonyl groups into hydroxy groups are simultaneously carried out by the catalyti hydrogenation. In this case, suitable conditions must be selected to avoid the hydrogenolysis of formed hydroxy group:
In these steps, catalysts of nickel, cobalt, platinum, coppe chromite, ruthenium and rhodium are generally used. As the catalyst carrier of them, activated carbon or alumina is emploed. Reaction media are not necessarily used in the reaction. If, however, they are used, alcohols such as ethy alcohol and saturated cyclic hydrocarbons such as cyclohexan are preferable. The reaction temperatures of the catalytic hydrogenation is in the range of 30 to 300°C and the reaction pressure is in the range of 2 to 300 kg/cm2.
In the reducing step of (I) represented in the foregoing reaction scheme, the carbon-carbon double bonds conjugated with the carbonyl group are selectively reduced to form the unconjugated ketone, which is further reduced to the hydroxy group by the same method as the step (G).
This selective reaction is performed by adding a solution of the unsaturated ketone in ethers such as diethyl ether, tetrahydrofran, dioxane and diethyleneglycol dimethylether and one equivalent or more of a proton donor such as ethanol or tert-butyl alcohol to a solution contain- ing more than two equivalents of sodium or lithium in liquid ammonia or alkyl amines such as ethylamine, n-propylamine and isopropylamine.
The reaction temperature of this partial reduction is ranging from -70 to 50°C, preferably -30 to 20°C.
The uncojugated ketone thus obtained is subjected to further
reduction to form the alcohol in the same manner as the
stop (G).
Through the above-described processes, the norbor-
nane derivatives represented by the foregoing general
formula (I) can be prepared.
The present invention is now further described
with reference to several examples. Example 1
Preparation of 5- or 6-ethylnorbornyl-2-aldehyde
A mixture of 2.5 g (0.011 mole) of glycidic
esters represented by the following formulae was dissolved
in 10 ml of methyl alcohol.
To the solution was added 2.5 g of 28% sodium methylate solution in methanol at a temperature below 20°C.
After that, 0.3 ml of water was added to the mixture
and hydrolysis was carried out by boiling the reaction mixture for 4 hours with stirring.
To the reaction mixture thus obtained were added
2 ml of concentrated hydrochloric acid and 6 ml of water
and decarboxylation was carried out with stirring the mixture
for 3 hours at 25 to 30°C. After the reaction, the reaction mixture was neutralized, rinsed with water and dried, and th solvents were distilled off..After that, 1.0 g of the
5- or 6-ethylnorbornyl-2-aldehyde was obtained in a yield of 60%. The boiling point of the product was
52 - 53°C/3.0 mmHg.
Other analytical data on the reaction product will be shown as follows: IR (Infrared spectrum analysis):
C-H stretching vibration of the aldehyde at 2,730 cm-1
and C=O stretching vibration of the aldehyde at
1,725 cm-1 were observed.
NMR (Nuclear magnetic resonance):
0.3 r (doublet, 1 H)
6.8 - 9.3 τ (multiplet, 15 H)
Elemental Analysis: (as C10H16O)
Example 2
Preparation of 5- or 6-vinylnorbornyl-2-aldehyde
A mixture of 2.5 g (0.011 mole) of glycidic
esters represented by.the following formulae was dissolved
in 10 ml of 99.5% ethyl alcohol.
To the solution was added 2.5 g of 28% sodium
methylate solution in methyl alcohol at a temperature below
20°C. After that, 0.3 ml of water was added to the
mixture and the glycidic esters were hydrolyzed by heating the reaction mixture to about 70°C for 3 hours with stirring.
To the reaction mixture thus obtained were added
1.2 ml of concentrated hydrochloric acid and 5.7 ml of water and decarboxylation was then carried out by refluxing the mixture for 3 hours. After this reaction, the reaction mixture was neutralized, rinsed with water and dried, and the solvent was distilled off. After that, 0.9 g of the
5- or 6-vinylnorbornyl-2-aldehyde was obtained in a yield of
54.5% by distillation under reduced pressure. The boiling point of the obtained product was 67°C/3.0 mmHg.
IR:
C-H stretching vibration of vinyl groups at 3,050 cm-1,
C=C stretching vibration of vinyl groups at 1,630 cm-1,
C-H stretching vibration of the aldehyde at 2,730 cm-1,
and C=O stretching vibration of the aldehyde at
1,725 cm-1 were observed.
NMR:
0.3 τ (singlet, 1 H)
4.1 T (multiplet, 1 H)
4.8 τ (multiplet, 2 H)
6.5 - 9.0 τ (multiplet, 10 H)
Elemental Analysis: (as C10H14O) Example 3
Preparation of 5- or 6-ethylidenenorbornyl-2-aldehyde
A mixture of 10.0 g (0.011 mole) of glycidic esters represented by the following formulae was dissolved in 50 ml of 99.5% ethyl alcohol.
Hydrolysis and decaroxylation were carried out in a manner similar to the foregoing Example 2 to obtain
3.2 g of 5- or 6-ethylidenenorbornyl-2-aldehyde in a yield of 48%. The boiling point of the obtained product was 84 - 87°C/10 mmHg.
IR:
C-H stretching vibration of the aldehyde at 2,710 cm-1,
C=O stretching vibration of the aldehyde at 1,725 cm-1,
C-H stretching vibration of ethylidene groups at
3,009 cm-1 and C=C stretching vibration of ethylidene
groups at 1,665 cm-1 were observed. NMR:
0.3 T (singlet, 1 H)
4.4 - 4.8 τ (multiplet, 1 H)
8.4 τ (doublet, 3 H)
6.5 - 9.1 τ (multiplet, 9 H) Elemental Analysis: (as C10H14O)
Example 4
Preparation of 3-methyl-5- or 6-ethylnorbornyl-2-aldehyde
In place of the glycidic esters used in Example 1,
0.011 mole of a mixture of the glycidic esters represented by the following two formulae was used. This mixture was treated in a manner similar to Example 1.
As a result, 3-methyl-5- or 6-ethylnorbornyl-
2-aldehyde was obtained in a yield of 55%. The boiling point
of this product was 48 - 51°C/2.0 mmHg.
IR:
C-H stretching vibration of the aldehyde at 2,730 cm-1,
and C=O stretching vibration of the aldehyde at
1,725 cm-1 were observed. NMR:
0.3 τ (doublet, 1 H)
6.5 - 9.0 τ (multiplet, 14 H)
9.1 T (doublet, 3 H)
Elemental Analysis: (as C11H18O)
Example 5
Preparation of 3-methyl-5- or 6-vinylnorbornyl-2-aldehyde
In place of the glycidic esters used in
Example 2, 0.011 mole of a mixture of the glycidic
esters represented by the following two formulae was used.
This mixture was treated in a like manner as Example 2.
As a result, 3-methyl-5- or 6-vinylnorbornyl-
2-aldehyde was obtained in a yield of 52.2%. The boiling
point of this product was 55 - 56°C/2.0 mmHg.
IR:
C-H stretching vibration of vinyl groups at 3,050 cm-1,
C=C stretching vibration of vinyl groups at 1,630 cm-1, C-H stretching vibration of the aldehyde at 2,730 cm-1 and
C=O stretching vibration of the aldehyde at 1,725 cm-1
were observed.
NMR:
0.3 τ (singlet, 1 H)
4.1 τ (multiplet, 1 H)
4.8 τ (multiplet, 2 H)
6.5 - 9.0 T (multiplet, 9 H)
9.1 T (doublet, 3 H)
Elemental Analysis: (as C11H16O)
Example 6
Preparation of 3,3-dimethyl-5- or 6-ethylidenenorbornyl-
2-aldehyde
In place of the glycidic esters used in
Example 3, 0.044 mole of a mixture of the glicidic esters represented by the following two formulae was used.
This mixture was treated in a like manner as Example 3. As a result, 3,3-dimethyl-5- or 6-ethylidene- norbornyl-2-aldehyde was obtained in a yield of 60.3%. The boiling point of this product was 66 - 69°C/3 mmHg.
IR:
C-H stretching vibration of ethylidene groups at 3,050 cm-1,
C=C stretching vibration of ethylidene groups at 1,675 cm-1,
C-H stretching vibration of the aldehyde at 2,725 cm-1 and
C=O stretching vibration of the aldehyde at 1,730 cm-1
were observed.
NMR:
Elemental Analysis: (as C12H18O).
Example 7-I
Preparation of 5- or 6-ethylnorbornyl-2-aldehyde
In a 200 ml autoclave was placed 5.0 g (0.033 mole)
of 5- or 6-vinylnorbornyl-2-aldehyde, 100 ml of ethyl alcohol,
and 0.2 g of 5% palladium-carbon catalyst and the autoclave
was then closed tightly. Then, degasification and
nitrogen gas displacement were repeated twice, the reaction was performed for one hour at room temperature with feeding hydrogen gas under pressure of 3 kg/cm2.
After the reaction was completed, the catalyst was removed by filtration from the reaction mixture and ethyl alcohol was recovered from the filtrate. The residue was distilled under reduced pressure to obtain 4.6 g of 5- or 6-ethyl- norbornyl-2-aldehyde in a yield of 91%.
The physical properties and analytical results of the compound thus obtained were all the same as those of the reaction product in Example 1.
Example 7-II
Preparation of 3-methyl-5- or 6-ethylnorbornyl-2-aldehyde
In place of 5- or 6-vinylnorbornyl-2-aldehyde
used as a starting material in Example 7-I, 5.0 g (0.030 mole)
of 3-methyl-5- or 6-ethylidenenorbornyl-2-aldehyde was used,
and it was treated in a like manner as Example 7-I.
As a result, the aimed 3-methyl-5- or 6-ethyl-
norbornyl-2-aldehyde was-obtained in a yield of 90%. The
physical properties and analytical results of this product
were all the same as those of the reaction product in
Example 4. Examples 8 to 25
In these Examples 8 to 25, the preparation of norbornyl-2-aldehydes having hydrocarbon side chains of the present invention were carried out through hydroformy- lation using carbon monoxide and hydrogen gas.
In these Examples, each norbornene, reaction medium and catalyst indicated in the following Table 1 were fed into a 500 ml autoclave and synthesis gas (CO/H2 = 1/1) was then charged under an elevated pressure. The reaction mixture in the. autoclave was allowed to react under the conditions of pressure, temperature and time shown in Table 1.
After the reaction was completed, the reaction mixture was cooled and excess unreacted gas was purged from the vessel.
After treating the contents in the autoclave with oxygen and hydrochloric acid, the organic layer was separated from the catalyst.' After the organic layer was washed with water and
dried, the reaction medium was recovered.and the residue was
then subjected to distillation under reduced pressure. The
obtained fraction was further purified by fractional
distillation to obtain a main fraction.
In connection with the main fraction, IR and NMR
spectrum analysis and elemental analysis were performed and
the yield of the main fraction was also determined.
The analytical data were compared with those in Examples 1 to
7-11 in order to identify the structures of the products.
The results of these Examples 8 to 25 are also
shown in the following Table 1.
In the Examples of Table 1, catalysts were as uniformly dispersed or dissolved as possible into the reaction mixture. In the case of Example 20, the use of
15 mmole of 10% chloro-rhodium-carbonyl complex
RhCl(CO)2P(C6H5)2 on silica powder, as a catalyst, gave almost the same result. It was observed that the yield of the aimed product is generally improved when the complex with phosphine ligand is used.
In Examples 10 and 19, even when cobalt hydro- carbonyl HCo(CO)4 was used in place of the cobalt carbonyl
Co2(CO)8, almost the same result was obtained. Further, in Examples 22 and 24, when rhodium carbonyl acetylacetonate was used in place of activated rhodium hydroxide Rh(OH)3 or rhodium carbonyl Rh4(CO)12, almost the same results were obtained.
Furthermore, when palladium hydroxide Pd(OH)2,
nickel carbonyl Ni(CO)4, nickel acetylacetonate Ni(C5-H7O)2
or iron carbonyl Fe(CO)5 was used as a catalyst, the yield
of the aimed product was decreased. Comparison of the
results of many other experiments leads to the fact that
cobalt and rhodium compounds are most preferable among group
VIII metals of periodic table. Iridium and ruthenium
compounds are also useful to some extent. Example 26
Preparation of 1-(5'- or 6'-ethylnorbornan-2'-yl)-2-
methylpentan-3-ol
Diethyl ketone, 32 g (0.37 mole) was dissolved in
150 ml of methyl alcohol and 5 g of 40% sodium hydroxide aqueous solution was further added thereto. To the mixture, -
21 g (0.14 mole) of a mixture of 5-vinylnorbornyl-2-aldehyde and 6-vinylnorbornyl-2-aldehyde was slowly added under reflux.
The aldol condensation was carried out by heating and refluxing this mixture for about 2 hours. In this reaction, since dehydration occurred simultaneously, no dehydration was needed. The reaction mixture was distilled under reduced pressure to give @,β-unsaturated ketone in a yield of 59%. With regard to this product, the existence of the carbonyl groups of the @,β-unsaturated ketone was confirmed by IR and NMR analysis, which indicated that the aldol condensation and subsequent dehydration were completed.
Then, 8.0 g (0.037 mole) of this a,ft-unsaturated ketone, 200 ml of ethyl alcohol and 0.3 g of 5% palladium- carbon powder were placed in a 1 liter autoclave. After clos- ing the autoclave, the contents were allowed to react under hydrogen pressure of 3 kg/cm .at room temperature for 2 hours.
Then the catalyst was removed from the reaction mixture and ethyl alcohol was distilled off. The residue was distilled under reduced pressure to afford a saturated ketone, in which the yield was 60.9% and the boiling point thereof was
101 - 102°C/1.5 mmHg. According to the analysis of this product, IR spectrum (neat) indicated the existence of the carbonyl group and NMR spectrum (CC14) indicated that all the protons
(4 H) in the olefinic region shifted toward the saturated hydrocarbon region.
This saturated ketone, 3.0 g (0.014 mole) was dissolved.in 10 ml of methyl alcohol, and 0.2 g of 15% potassium hydroxide aqueous solution was added to that
solution. Then, a solution of sodium borohydride prepared
by mixing 0.30 g of NaBH4, 0.02 g of potassium hydroxide,
2.0 ml of water and 2.0 ml of methyl alcohol was added to
the reaction mixture with stirring at about 40°C.
The reaction mixture thus prepared was stirred for additional
3 hours. Then, methyl alcohol was distilled off under reduced
pressure from the mixture and the residue was extracted with
ether. After the extract was washed twice with water and
dried, it was subjected to distillation under reduced pressure
to obtain 2.8 g of 1-(5'- or 6'-ethylnorbornan-2'-yl)-2-
methylpentan-3-ol in a yield of 89.3%. This product had
a boiling point of 120 - 121°C/1.5 mmHg and was a viscous
liquid having woody odor with green tone.
IR: cm O-H stretching vibration was observed at 3,400 and
the absorption of the ketone disappeared by reduction. NMR: (CDCl3)
6.3 τ (triplet, 1 H)
6.8 r (broad singlet, 1 H)
7.5 r (broad singlet, 1 H)
7.8 - 9.3 τ (multiplet, 25 H)
Elemental Analysis: (as C15H28O)
Example 27
Preparation of 1-(5'- or 6'-ethylnorbornan-2'-yl)-2-methyl-
1-penten-3-ol
The aldol condensation was carried out in a like manner as Example 26 by using 2.1 g (0.014 mole) of a mixture
of 5-ethylnorbornyl-2-aldehyde and 6-ethylnorbornyl-2-aldehyde
and diethyl ketone. Concurrent dehydration was allowed to
occur to obtain @,β-unsaturated ketone in a yield of 55%.
With regard to this product, the existence of the carbonyl
group of the @,β-unsaturated ketone was confirmed by IR and
NMR analysis, which indicated that the aldol condensation
and subsequent dehydration were completed.
Then, 1.5 g (0.007 mole) of this unsaturated ketone
was dissolved in a mixture of methyl alcohol and potassium
hydroxide. A solution of sodium borohydride prepared by
mixing 0.13 g of NaBH4, 0..01 g of potassium hydroxide, 1.0 ml
of water and 1.0 ml of methyl alcohol was added to the reaction mixture with stirring at about 40°C. The obtained mixture was stirred for additional 3 hours.
After the reaction was completed, methyl alcohol was distilled off and the residue was sufficiently washed with water and dried and then distilled under reduced pres- sure to obtain 1.3 g of 1-(5'- or 6'-ethylnorbornan-2'-yl)-
2-methyl-l-penten-3-ol in a yield of 84%. This reaction product had a boiling point of 124 - 126°C/2.0 mmHg and was a colorless oily substance having warm and sweet woody odor.
IR:
O-H stretching vibration was observed at 3,400 cm-1 and
the absorption of the carbonyl groups of @,β-unsaturated
ketone at 1,660 cm-1 was lost through reduction.
NMR: (CDCl3)
4.7 - 4.8 T (doublet, 1 H)
6.1 - 6.3 T (triplet, 1 H)
8.4 τ (singlet, 3 H)
7.5 - 9.3 τ (multiplet, 21 H)
Elemental Analysis: (as C15H26O) Example 28
Preparation of 1-(3'-methyl-5'- or 6'-ethylnorbornan-2'-yl)-
2-methylpentan-3-ol
The aldol condensation was carried out in a like manner as Example 26 with 5.0 g (0.030 mole) of a mixture of
3-methyl-5-ethylidenenorbornyl-2-aldehyde and 3-methyl-6- ethylidenenorbornyl-2-aldehyde and diethyl ketone, which was followed by dehydration. Thus @,β-unsaturated ketone was obtained in a yield of 57% and its structure was confirmed by IR and NMR analysis.
In a 500 ml autoclave were then placed 4.0 g.(0.017 mole) of this @,β-unsaturated ketone, 100 ml of ethyl alcohol, and 0.2 g of 5% rhodium-alumina catalyst. After the autoclave was closed up, the contents were allowed to react at about 50°C under hydrogen pressure of 4 kg/cm2 for 6 hours, in which about 150 ml of hydrogen gas was absorbed. After the removal of the catalyst, the ethyl alcohol was distilled off and the residue was distilled under reduced pressure to obtain the above 1-(3'-methyl-5'- or 6'-ethylnorbornan-2'-yl)-2-methylpentan-
3-ol having a boiling point of 126 - 129°C/2.0 mmHg in a yield of 78.0%. This product was a colorless oily substance having refreshing woody odor. IR: cm-1 0-H stretching vibration at 3,400 was observed
and the characteristic absorptions of carbon-carbon
double bonds and @,β-unsaturated ketone (C=C at 1,640 cm-1
and C=O at 1,660 cm ) were lost by reduction. NMR: (CDC13)
6.3 τ (triplet, 1 H)
6.8 r (broad singlet, 1 H)
7.5 - 9.4 T (multiplet, 28 H)
Elemental Analysis: (as C16H30O)
Example 29
Preparation of 1-(3',3'-dimethyl-5'- or 6'-ethylnorbornan-
2'-yl)-2-methyl-1-penten-3-ol and
1-(3',3'-dimethyl-5'- or 6'-ethylnorbornan-
2'-yl)-2-methylpentan-3-ol
Aldol condensation and dehydration were carried out
with 10.0 g (0.056 mole) of a mixture of 3,3-dimethyl-5-
ethylnorbornyl-2-aldehyde and 3,3-dimethyl-6-ethylnorbornyl-
2-aldehyde and diethyl ketone, in a like manner as Example 26
to obtain @,β-unsaturated ketone in a yield of 60%. The
structure of this ketone was identified by IR and NMR
analysis.
The unsaturated ketone, 5.0 g (0.020 mole) was reduced
by using sodium borohydride in a like manner as Example 27 to
obtain 4.3 g of l-(3',3'-dimethyl-5'- or 6'-ethylnorbornan-
2'-yl)-2-methyl-1-penten-3-ol in a yield of 85.3%. This
product had a boiling point of 122 - 125°C/1.7 mmHg and was
a colorless oily substance having flowery woody odor. IR:
O-H stretching vibration at 3,360 cm-1 was observed
and the absorption (1,660 cm-1) of the carbonyl group of
@,β-unsaturated ketone was lost by reduction.
NMR: (CDC13)
4.7 - 4.8 τ (doublet, 1 H)
6.2 - 6.3 τ (triplet, 1 H)
8.3 τ (singlet, 3 H)
7.4 - 9.4 t (multiplet, 25 H)
Elemental Analysis: (as C17H300)
In a 500 ml autoclave were placed 3.0 g (0.012 mole) of the above product, 100 ml of ethyl alcohol and
0.1 g of 5% palladium-carbon catalyst and the autoclave was closed. The contents were reacted at room temperature under hydrogen pressure of 2 kg/cm2 and the reaction was stopped when about 270 ml of hydrogen gas was absorbed. The catalyst was removed from the reaction mixture and ethyl alcohol was distilled off. The residue was then distilled under reduced pressure to obtain 2.6 g of
1-(3',3'-dimethyl-5'- or 6'-ethylnorbornan-2'-yl)-2-methyl- pentan-3-ol in a yield of 86.0%. This product had a boiling point of 121 - 124°C/1.3 mmHg and was a colorless oily substance having woody odor with green tone. IR: cm-1 O-H stretching vibration at 3,360 was observed
and the absorption of C=C stretching vibration of carbon- cm-1 carbon double bonds at 1,640 was lost by the
hydrogenation.
NMR: (CDC13)
Elemental Analysis: (as C17H32O)
Example 30
Preparation of 1-(5'- or 6'-vinylnorbornan-2'-yl) -2-methyl-
1-penten-3-ol
Diethyl ketone, 3.2 g (.0.037 mole) was dissolved
in 15 ml of methyl alcohol and 0.5 g of 40% sodium hydroxide
solution was added thereto. To the mixture, 2..1 g (0.014 mole)
of a mixture of 5-vinyl-norbornyl-2-aldehyde and 6-vinyl-
norbornyl-2-aldehyde was slowly added under reflux.
The aldol condensation was carried out by refluxing
this mixture for additional 2 hours.. Since dehydration
occurred simultaneously, no dehydration process was employed. The reaction mixture was distilled under reduced preessure to obtain @,β-unsaturated ketone in a yield of 59%. In the
IR and NMR spectrum analysis of this product, the existence of the carbonyl group of the @,β-unsaturated ketone indicatec the completion of the aimed reaction.
Then, 1.5 g (0.007 mole) of this unsaturated ketone was dissolved in a mixture of methyl alcohol and potassium hydroxide. With stirring and heating to about 40°C, a soluti: of sodium borohydride (NaBH4 0.13 g + KOH 0.01 g + water
1.0 ml + methanol 1.0 ml) was added, which was followed by
3 hours' stirring. After the reaction was completed, methyl alcohol was distilled off from the reaction mixture and wash with water and dried. It was then distilled under reduced pressure to obtain 1.3 g of 1-(5'- or 6'-vinylnorbornan-2'-y
2-methyl-l-penten-3-ol in a yield of 85%. This product had a boiling point of 110 - 113°C/0.8 - 1.1 mmHg and was a
colorless oily substance having warm woody odor.
IR:
0-H stretching vibration at 3,400 cm-1,
C-H stretching vibration of the vinyl group at 3,090 cm
and C=C stretching vibration of the vinyl group at
1,640 cm-1 were observed, while.the absorption of the 1,670 cm-1 carbonyl group of @,β-unsaturated ketone at
was lost by reduction.
NMR: Elemental Analysis: (as C15H24O)
Example 31
Preparation of 1-(5'- or 6'-ethylidenenorbornan-2'-yl)-
2-methyl-l-penten-3-ol
To 20 ml of 4.6 g (0.053 mole) diethyl ketone
solution in methyl alcohol, 0.7 g of 40% sodium hydroxide
solution was added. Then, to the mixture, 3.0 g of a
mixture of 5-ethylidenenorbornyl-2-aldehyde and
6-ethylidenenorbornyl-2-aldehyde was added dropwise under
reflux. After the dropwise addition was completed, the
refluxing was continued for additional 2 hours and methyl
alcohol was then distilled off, thereby obtaining
@,β-unsaturated ketone in a yield of 60% through distillatior
under reduced pressure. By IR and NMR analysis of this
product, the existence of the carbonyl group of the
@,β-unsaturated ketone indicated the completion of the
aimed reaction. Then, 3.0 g (0.014 mole) of this @,β-unsaturated ketone was dissolved in a mixture of methyl alcohol and potassium hydroxide. With stirring and heating to about 40°C, a solution of sodium borohydride (NaBH4 0.26 g + KOH 0.02 g
+ water 2.0 ml + methanol 2.0 ml) was added to the above solution and additional stirring was continued for 4 hours.
After the reaction was completed, methyl alcohol was distilled off from the reaction mixture and washed with water and dried.
It was then distilled under reduced pressure to obtain
1-(5'- or 6'-ethylidenenorbornan-2'-yl)-2-methyl-l-penten-3-ol in a yield of 66%. This product had a boiling point of
114 - 116°C/0.8 - 0.9 mmHg and was a colorless oily substance having favorable woody odor with quite fresh green tone.
IR:
O-H stretching vibration at 3,400 cm-1, and
C-H stretching vibration at 3,090 cm-1 and
C=C stretching vibration at 1,640 cm of ethylidene
group were observed but the absorption of the carbonyl cm group of @,β-unsaturated ketone at 1,670 was
lost by the reduction.
NMR: Elemental Analysis: (as C15H240)
Example 32
Preparation of 1-(3'-methyl-5'- or 6'-vinylnorbornan-2'-
yl)-2-methyl-1-penten-3-ol
The preparation was carried out in a like manner as
the foregoing Example 30 except that 3-methyl-5- or 6-vinyl-
norbornyl-2-aldehyde was used in place of the foregoing
.vinylnorbornyl-2-aldehyde, thereby obtaining @,β-unsaturated
ketone in a yield of 62%. It was then reduced likewise to
obtain the above compound, 1-(3'-methyl-5'- or 6'-vinyl-
norbornan-2'-yl)-2-methyl-1-penten-3-ol in a yield of 82%.
This product had a boiling point of
115 - 120°C/1.2 mmHg and was a colorless oily substance
having favorable warm woody odor.
IR: . O-H stretching vibration at 3,400 cm-1, and
C-H stretching vibration at 3,090 cm-1 and C=C stretching
vibration at 1,640 cm-1 of the vinyl group were observed
but the absorption of the carbonyl group of @,β-unsaturated
ketone at 1,670 cm-1 was lost by reduction.
NMR: Elemental Analysis: (as C16H260)
Example 33.
Preparation of 1-(3'-methyl-5'- or 6'-ethylidenenorbornan-
2'-yl)-2-methyl-l-penten-3-ol
The preparation was carried out in a like manner as the foregoing Example 30 except that 3-methyl-5- or 6- ethylidenenorbornyl-2-aldehyde was used in place of the foregoing vinylnorbornyl-2-aldehyde, thereby obtaining
@,β-unsaturated ketone in a yield of 58%. It was then reduced likewise to obtain the above compound, l-(3'-methyl-
5'- or 6'-ethylidenenorbornan-2'-yl)-2-methyl-l-penten-3-ol in a yield of 85%.
This product had a boiling point of
117 - 122°C/1.1 mmHg and was a colorless oily substance having woody odor with vetiver tone. IR:
O-H stretching vibration at 3,400 cm-1, and
cm-1 C-H stretching vibration at 3,090 and C=C stretching cm-1 vibration at 1,640 of the ethylidene group were
observed but the absroption of the carbonyl group of cm-1 a,ft-unsaturated ketone at 1,670 was lost by reduction.
NMR:
Elemental Analysis: (as C16H260)
Example 34
Preparation of 1-(3',3'-dimethyl-5'- or 6'-ethylidene-
norbornan-2'-yl)-2-methyl-l-penten-3-ol
The preparation was carried out in a like manner as
the foregoing Example 30 except that 3,3-dimethyl-S- or 6-
ethylidenenorbornyl-2-aldehyde was used in place of the vinyl
norbornyl-2-aldehyde, thereby obtaining a,β-unsaturated
ketone in a yield of 64%. It was then reduced likewise to obtain 1-(3',3'-dimethyl-5'- or 6'-ethylidenenorbornan-2'- yl)-2-methyl-l-penten-3-ol in a yield of 78%.
This product had a boiling point of 122 - 126°C/0.8 mmHg and was a colorless oily substance having woody odor with fougere tone.
IR:
O-H stretching vibration at 3,400 cm-1, and
C-H stretching vibration at 3,090 cm-1 and C=C stretching
vibration at 1,640 cm-1 of the ethylidene group were
observed but the absorption of the carbonyl group of
@,β-unsaturated ketone at 1,670 cm-1 was lost by
reduction.
Elemental Analysis: (as C17H280) Example 35
Preparation of 4-(5'- or 6'-vinylnorbornan-2'-yl)-3-methyl-
3-buten-2-ol
The preparation was carried out in a like manner as the foregoing Example 30 except that 2.7 g (0.037 mole) of methyl ethyl ketone was used in place of diethyl ketone.
Through fractional distillation, the aldol condensation product of @,β-unsaturated ketone, 4-(5'- or 6'-vinyl- norbornan-2'-yl)-3-methyl-3-buten-2-on was obtained in a yield.of 35%. Then, the reduction in a like manner as Example
30 afforded 4-(5'- or 6'-vinylnorbornan-2'-yl)-3-methyl-3-
buten-2-ol in a yield of 80%.
This product had a boiling point of 103 - 106°C/
0.9 mmHg and was a colorless oily substance having woody odor
with fugere tone.
IR:
O-H stretching vibration at 3,400 cm-1, and
C-H stretching vibration at 3,090 cm-1 and C=C stretching cm-1 vibration at 1,640 of the vinyl group were observed
but the absorption of the carbonyl group of @,β-unsaturated
ketone at 1,670 cm-1 was lost by reduction.
NMR: Elemental Analysis: (as C14H220)
Example 36
Preparation of Portugal aldehyde
The ethylnorbornyl-2-aldehyde prepared in Example 1 was formulated in the following composition to provide a
Portugal aldehyde-
This Portugal aldehyde is suitable for use in formulating a citrus perfume or an orange flavor. Example 37
Preparation of greenish Portugal aldehyde
In the formulation of Example 36, the ethylnorbornyl-
2-aldehyde was replaced by the ethylidenenorbornyl-2-aldehyde prepared in Example 3, to give a greenish Portugal aldehyde.
When this Portugal aldehyde is formulated in citrus perfume or chpre perfume, the note is converted more fresh or green.
Example 38
Preparation of red rose base perfume
The norbornane derivative prepared in Example 26,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2-methylpentan-3-ol was formulated in the following composition to provide red rose base.
This base perfume is suitable for use in formulating
a floral bouquet perfume in a very sweet rose note. Further,
it is generally used as the main ingredient of room interior
perfumes and attar of rose. Example 39
Preparation of white rose base perfume
The norbornane derivative prepared in Example 27,
1-(5'- or 6'-ethylnorbornan-2'-yl)-2-methyl-l-penten-3-ol was formulated in the following composition to provide a white rose base.
This base perfume is suitable for use in preparing formulated perfumes in refreshing white rose note.
In addition, it may be widely used as a perfume ingredient for preparing pastiness and powder cosmetics. Example 40
Preparation of cypre base perfume
The norbornane derivative prepared in Example 28,
1-(3'-methyl-5'- or 6'-ethylnorbornan-2'-yl)-2-methylpentan- to provide a 3-ol was formulated in the following composition cypre base.
is suitable for use in This cypre base perfume interior preparing hair cosmetics and room perfumes. Example 41
Preparation of fougere woody perfume
The norbornane derivative prepared in Example 29,
1-(3',3'-dimethyl-5'- or 6'-ethylnorbornan-2'-yl)-2-methyl- pentan-3-ol was formulated in the following composition
to provide a fougere woody base.
This fougere woody perfume is quite suitable in preparing cosmetics for men, for example, Eau de cologne. Example 42
Preparation of oriental cypre perfume
The norbornane derivative, 1-(3'-methyl-5'- or 6'- ethylnorbornan-21-yl)-2-methyl-l-penten-3-ol prepared by
reduction of the @,β-unsaturated ketone in Example 28, was
formulated in the following composition to provide a base
perfume in oriental cypre note.
This perfume gives favorable fragrance but it
is dark-colored, so that it is not suitable for cosmetics.
It is, however, quite suitable as fragrant ingredient for
shoe polish, mosquito-repellent mats, deodorants, insecticides,
and the like with markable effect. Example 43
Preparation of sandalwood base perfume
The red rose base perfume prepared in Example 38 and the white rose base perfume prepared in Example 39 were formulated in the following composition to provide a sandalwood base perfume.
This base perfume has fantastic sandalwood fragrance and
its alcoholic solution can be used for perfuming folding fans.
Further, it can be used for preparing room interior deodorant
composition.
Example 44
Preparation of fougere perfume
The norbornane derivative that was prepared in
Example 30 was formulated in the following composition to
provide a fougere perfume. This perfume can be used as a base perfume for toiletries as well as soaps.
Example 45
Preparation of oriental rose perfume
The norbornane derivatives prepared in Examples 30 and 31 were formulated in the following composition to provide an oriental rose perfume. This composition is Persian Gulistan perfume and attar of rose is prepared by diluting it with aqueous alcohol solution. It is solidified with carrageenin gel, and the solid can be used as room fragrance having oriental rose odor.
Example 46
Preparation of narcissus perfume (I)
The norbornane derivative prepared in Example 33
was formulated in the following composition to provide
a narcissus perfume. This narcissus perfume gives fresh fragrance and used for preparing perfumes for detergents, bath salts and artificial flower aromatics.
Example 47
Preparation of narcissus perfume (II)
In the formula of Example 46, the norbornane derivative prepared in Example 33 was replaced by the norbornane derivative prepared in Example 34, where the narcissus perfume was imparted with fantastic tone.
This composition is suitable for use as odor ingredient for preparing perfumes used in rooms or cars. 1. A norbornane derivative having hydrocarbon side chain which is represented by the following general formula (I)
wherein C2 is an ethyl group, an ethylidene group or a vinyl
group each connected to 5 or 6 position of the norbornane
ring, the dashed line connected to C2 is a single bond when
C2 is an ethyl group or a vinyl group and a double bond when
C2 is an ethylidene group, each of R1 and R2 is a hydrogen
atom or a methyl group, and R3 is a formyl group or a group
represented by the following general formula (II)
wherein R4 is a methyl group, an ethyl group, a n-propyl grou
or an isopropyl group, the combination of a solid line with
a dotted line indicates a single bond or a double bond, and
X is a carbon atom of the norbornane ring. 2. The norbornane derivative in Claim 1, wherein said compound is one member selected from the group consisting of 5- or 6-ethyl-, 5- or 6-ethylidene-, 5- or 6-vinyl- norbornyl-2-aldehyde, and their 3-methyl or 3,3-dimethyl derivatives.
3. The norbornane derivative in Claim 1, wherein said compound is one member selected from the group consisting of 4-(5'- or 6'-ethyl-, 4-(5'- or 6'-ethylidene-,
4-(5'- or 6'-vinyl-norbornan-2'-yl)-3-methylbutan-2-ol, and their 3'-methyl or 3',3'-dimethyl derivatives.
4. The norbornane derivative in Claim 1, wherein said compound is one member selected from the group consisting of 4-(5'- or 6'-ethyl-, 4-(5'- or 6'-ethylidene-,
4-(5'- or 6'-vinyl-norbornan-2'-yl)-3-methyl-3-buten-2-ol,
and their 3'-methyl or 3',3'-dimethyl derivatives.
5. The norbornane derivative in Claim 1, wherein
said compound is one member selected from the group consisting
of 1-(5'- or 6'-ethyl-, 1-(5'- or 6'-ethylidene-,
1-(5'- or 6'-vinyl-norbornan-2'-yl)-2-methylpentan-3-ol,
and their 3'-methyl or 3',3'-dimethyl derivatives. 6. The norbornane derivative in Claim 1, wherein
said compound is one member selected from the group consisting of 1-(5'- or 6'-ethyl-, 1-(5'- or 6'-ethylidene-,
1-(5'- or 6'-vinyl-norbornan-21-yl)-2-methyl-l-penten-3-ol,
and their 3'-methyl or 3',3'-dimethyl derivatives.
7. The norbornane derivative in Claim 1, wherein
said compound is one member selected from the group consisting
of 1-(5'- or 6'-ethyl-, 1-(5'- or 6'-ethylidene-,
1-(5'- or 6'-vinyl-norbornan-2'-yl)-2,4-dimethylpentan-3-ol,
and their 3'-methyl or 3',3'-dimethyl derivatives.
8. The norbornane derivative in Claim 1, wherein
said compound is one member selected from the group consisting
of 1-(5'- or 6'-ethyl-, 1-(5'- or 6'-ethylidene-,
1-(5'- or 6'-vinyl-norbornan-2'-yl)-2,4-dimethyl-l-penten-3-ol,
and their 3'-methyl or 3',3'-dimethyl derivatives.
9. The norbornane derivative in Claim 1, wherein
said compound is one member selected from the group consisting
of 1-(5'- or 6'-ethyl-, 1-(5'- or 6'-ethylidene-,
1-(5'- or 6'-vinyl-norbornan-2'-yl)-2-methylhexan-3-ol,
and their 3'-methyl or 3',3'-dimethyl derivatives. 10. The norbornane derivative in Claim 1, wherein said compound is one member selected from the group consisting of 1-(5'- or 6'-ethyl-, 1-(5'- or 6'-ethylidene-,
1-(5'- or 6'-vinyl-norbornan-2'-yl)-2-methyl-l-hexen-3-ol, and their 3'-methyl or 3',3'-dimethyl derivatives.
. 11. A method for preparing a norbornane derivative of the following general formula (I-I)
wherein C2 is an ethyl group, an ethylidene group or a vinyl group each connected to 5 or 6 position of the norbornane
ring, the dashed line connected to C2 is a single bond when
C2 is an ethyl group or a vinyl group and a double bond when
C2 is an ethylidene group, and each of R1 and R2 is a
hydrogen atom or a methyl group,
said method being characterized in hydrolyzing
and decarboxylating a glycidic ester represented by the
following general formula (III) at temperatures in the
range of 0 to 250°C,
the wherein C2, dashed line, R1 and R2 are respectively same
as those in the foregoing formula (I-I) and R5 is a
hydrocarbon group having 1 to 6 carbon atoms. 12. A method for preparing a norbornane derivative
' of the following general formula (I-I)
wherein C2 is an ethyl group, an ethylidene group or a vinyl
group each connected to 5 or 6 position of the norbornane
ring, the dashed line connected to C2 is a single bond when
C2 is an ethyl group or a vinyl group and a double bond when
C2 is an ethylidene group, and each of R1 and R2 is a .
hydrogen atom or a methyl group,
said method being characterized in that
2-norbornene represented by the following general formula (IV)
is reacted with carbon monoxide and hydrogen gas in the
presence of a catalyst at temperatures in the range of
30 to 300°C
wherein C2, dashed line and R1 are respectively the same
as those in the foregoing general formula (I-I). 13. The method for preparing a norbornane derivative in Claim 12, wherein said catalyst is a compound of group VIII elements of the periodic table.
14. The method for preparing a norbornane derivative in Claim 12 or 13, wherein said catalyst is at least one member
selected from the group consisting of the compounds of cobalt, rhodium, iridium, ruthenium and platinum. 15. A method for preparing a norbornane derivative of the following general formula (I-II)
wherein each of R1 and R2 is a hydrogen atom or a methyl group,
said method being characterized in that the corresponding norbornane derivative of the general formula
(I-III) is partially hydrogenated
wherein C2 is an ethylidene group or a vinyl group each
connected to 5 or 6 position of the norbornane ring, the
dashed line connected to C2 is a single bond when C2 is
a vinyl group and a double bond when C2 is an ethylidene
group and each of R1 and R2 is a hydrogen atom or a methyl group. 16. A method for preparing a norbornane derivative
of the following general formula (I-IV)
wherein C2 is an ethyl group, an ethylidene group or a vinyl
group each connected to 5 or 6 position of the norbornane
ring, the dashed line connected to C2 is a single bond when
C2 is.an ethyl group or a vinyl group and a double bond when
C2 is an ethylidene group, each of R1 and R2 is a hydrogen
atom or a methyl group,, and R3 is a group represented by the
following general formula (II)
wherein R4 is a methyl group, an ethyl group, a n-propyl group
or an isopropyl group, the combination of a solid line with
a dotted line indicates a single bond or a double bond, and
X is a carbon atom of the norbornane ring,
said method is characterized in that a norbornane
derivative represented by the general formula (I-I) is
reacted with an ethyl alkyl ketone in the presence of an aldol
condensation catalyst at a temperature in the range of
0 to 200°C, which is followed by dehydration and reduction, wherein C2, dashed line, R1 and R2 are the same as those of the foregoing general formula (I-IV).
17. The method for preparing a norbornane derivative in Claim 16, wherein said ethyl alkyl ketone is at least one member selected from the group consisting of methyl ethyl ketone, diethyl ketone, ethyl propyl ketone and ethyl isopropyl ketone. 18. 'A perfume composition containing a compound represented by the following general formula (I)
wherein C2 is an ethyl group, an ethylidene group or a vinyl
group each connected to 5 or 6 position of the norbornane
ring, the dashed line connected to C2 is a single bond when
C2 is.an ethyl group or a vinyl group and a double bond when
C2 is an ethylidene group, each of R1 and R2 is a hydrogen
atom or a methyl group, and R3 is a formyl group or a group
represented by the following general formula (II)
wherein R4 is a methyl group, an ethyl group, a n-propyl group
or an isopropyl group, the combination of a solid line with
a dotted line indicates a single bond or a double bond, and
X is a carbon atom of the norbornane ring.